DE2806834A1 - Insecticidal agents contg. dioxolanyl-methyl-benzodioxole derivs. - with insect development inhibiting activity - Google Patents

Abstract

New insecticidal agents contain benzodioxole derivs. of formula (I): (where R' and R2 are H, alkyl, alkenyl, alkynyl or aryl, or R' + r2 is alkylene. (I) are inhibitors of the development of insects and mites, and may be used to control such pests in agriculture, forestry, stored products and materials protection, and the hygiene sector. (I) may be made up into conventional formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granulates, aerosols, emulsifiable concentrates, seed dressings etc. Formulations generally contain 0.1-95 (pref. 0.5-90) wt. % (I).

Description

Insecticidal agents

The present invention relates to the use of benzodioxole derivatives as an insect development inhibitor.

It has been found that the benzodioxole derivatives of the formula (I) in which R¹ and R² can be the same or different and represent H, alkyl, alkenyl, alkynyl and aryl or R¹ and R² together represent an alkylene group inhibit the development of insects.

These compounds can be prepared by adding a compound of Formula II in which X stands for OH or both radicals X stand for -0-, with a carbonyl compound of the general formula III in which R and R2 have the meaning given above, optionally reacted in the presence of a diluent.

The benzodioxole derivatives inhibiting the development of insects are generally defined by the formula (I).

Preferably, however, are in the formula (I) R1 and R2 for hydrogen, straight-chain or branched alkyl or alkenyl with up to 10 carbon atoms, as well as optionally substituted phenyl or R¹ and R² together for a straight-chain or branched alkyl chain with up to 10 carbon atoms.

Specific examples are: 5- (3,4-methylenedioxybenzyl) dioxolane 2-methyl-5- (3,4-methylenedioxybenzyl) dioxolane, 2-ethyl-5- (3,4-methylenedioxybenzyl) dioxolane 2-n-Propyl-5- (3,4-methylenedioxybenzyl) -dioxolane. 2-i-Propyl-5- (3.4-methylenedioxybenzyl) -dioxolane 2-n -Butyl-5- (3,4-methylenedioxybenzyl) dioxolane. 2-i-Butyl-5- (3,4-methylenedioxybenzyl) dioxolane 2-t -Butyl-5- (3,4-methylenedioxybenzyl) -dioxolane, 2-Allyl-5- (3,4-methylenedioxybenzyl) -dioxolane 2-methallyl-5- (3,4-methylenedioxybenzyl) dioxolane, 2-crotyl-5- (3,4-methylenedioxybenzyl) dioxolane 2-ethynyl-5- (3,4-methylenedioxybenzyl) dioxolane 2-phenyl-5- (3,4-methylenedioxybenzyl) dioxolane 2- (3.4-Methilenedioxyphenyl) -5- (3.4-methylenedioxybenzyl) dioxolane 2,2-dimethyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-methyl-2-ethyl-5- (3,4-methylenedioxybenzyl) dioxolane, 2-methyl-2-n-propyl-5- (3,4-methylenedioxybenzyl) dioxolane 2-methyl-2-i-propyl-5- (3.4-methylenedioxybenzyl) dioxolane, 2-methyl-2-n-butyl-5- (3,4-methylenedioxybenzyl) dioxolane 2-methyl-2-i-butyl-5- (3.4-methylenedioxybenzyl) dioxolane 2-methyl-2-t-butyl-5- (3,4-methylenedioxybenzyl) dioxolane 2,2-diethyl-5- (3,4-methylenedioxybenzyl) dioxolane 2,2-di-n-propyl-5- (3,4-methylenedioxybenzyl) dioxolane 2,2oDi-n-butyl-5- (304-methylenedioxybenzyl) -dioXolane, 2-methyl-2-phenyl-5- (3,4-methylenedioxybenzyl) -dioxolane 2-Spirocyclohexane-5- (3,4-methylenclio.ybenzyl) -dioXolane 2-Spirocyclohexane-5- (3,4-methylenedioxybenzyl) -dioxolane 2- (2,4,4-Trimethyl-spirocyclohexane-5- (3,4-methylenedioxybenzyl) -dioxolane In the as starting compounds for the preparation of the benzodioxole derivatives which can be used according to the invention Serving compounds of the formula II are 3- (3,4-methylenedioxyphenyl) -propanediol-1,2 and around 3,4-methylenedioxybenzylethylene oxide. Both connections are known as well like the carbonyl compounds of the formula III.

The process for the preparation of the compounds which can be used according to the invention is optionally with the use of suitable solvents or diluents carried out. Practically all inert organic solvents can be used as such. this includes in particular aliphatic and aromatic, optionally chlorinated, Hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform and carbon tetrachloride.

In the event that X stands for OH, one works in the presence of acidic Catalysts, such as sulfuric acid or p-toluenesulphonic acid and in the event that that the two X stand for an oxygen atom, one works in the presence of one Catalyst such as boron trifluoride.

The reaction temperature can vary within a relatively wide range will. In general, one works between 25 and 1500C, preferably between 70 and 1200C.

The reaction is generally allowed to proceed under normal pressure.

When using 3- (3,4-methylenedioxyphenyl) 1,2-propanediol, the process is carried out as the starting product, the carbamoyl compounds, preferably in equimolar amounts a. An excess of one or the other reaction component does not bring about any significant Advantages. In general, the two reaction components are in one of the specified Solvent in the presence of an acidic catalyst at the given temperatures implemented. The resulting water is removed by azeotropic distillation If 3,4-methylenedioxybenzylethylene oxide is used as the starting component, so is a preferred embodiment that the larbonyl component is used in excess and thus serves as a reaction component and solvent. The implementation takes place preferably in the presence of one of the specified catalysts for the specified Temperatures. After the reaction has ended, it is worked up as usual Shaking out with an organic solvent, washing, drying the organic Phase and distilling off the solvent.

The compounds according to the invention are characterized by their boiling point.

The benzodioxole derivatives which can be used according to the invention show a good the development of insects and arachnids inhibiting effect on animal pests, in particular insects that are used in agriculture, in forests, in storage and aluminum material protection as well as in the hygiene sector. They are sensitive and resistant to normal Species effective. The pests mentioned include: Out of order the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda e.g. Blaniulus qttulatus.

From the order of the Chilopoda, e.g. Geophilus carpophaus and Scutigera spec.

From the order of the Symphyla, e.g. Scutigerella immaculata.

From the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Collembola, e.g. Onychiurus armatus.

From the order of the Orthoptera, e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera, e.g. Forficula auricularia.

From the order of the Isoptera, e.g. Reticulitermes spp ..

From the order of the Anoplura e.g. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga, for example Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera, e.g. Hercinothrips fermoralis, Thrips tabaci.

From the order of the Heteroptera, e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera, e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.

From the order of the Lepidoptera, e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp, Euxoa spp., Feltia spp. Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera, e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, nqriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles sps., Culex spp., Drosophila melanooaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera, e.g. Xenopsylla.cheopis, Ceratophyllus spp ..

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, Pastes, soluble powders, granulates, aerosols, suspension emulsion concentrates, Seed powder, active ingredient-impregnated natural and synthetic substances, ultra-fine encapsulation in polymeric substances and in coating compounds for seeds, also in formulations with Burning sets, such as smoking cartridges, cans, coils, etc. as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for example by Mixing the active ingredients with extenders, i.e. liquid solvents, under Liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents. In the case of using water as an extender For example, organic solvents can also be used as auxiliary solvents. The following liquid solvents are essentially: aromatics, such as xylene, Toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic Hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers are meant liquids which are at normal temperature and are gaseous under normal pressure, e.g. aerosol propellants,> -the halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers come into question: e.g. natural rock flour, such as kaolins, clays, talc, chalk, Quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates; as solid carriers fü: Granules are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granulates made from inorganic and organic flours as well as granulates made of organic material such as sawdust, coconut shells, Corn cobs and tobacco stalks; come as emulsifying and / or foam-reducing agents in question: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl pelyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azole-metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, ivobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention are used in the form of them commercial formulations and / or those prepared from these formulations Application forms.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary within wide ranges. The active ingredient concentration the use forms can range from 0.0000001 to 100% by weight of active ingredient, preferably between 0.01 and 10 wt .-%.

They are used in a customary manner adapted to the use forms Way.

In the following examples of the development-inhibiting effect of Active ingredients are used throughout the specified development of the test animals morphological changes, such as half-pupated animals, incompletely hatched Larvae or caterpillars, defective wings, pupal cuticles in adults, etc., as malformations rated.

The sunmle of the morphological malformations, along with the during of the molting process or the metamorphosis of killed animals is in percent the total number of test animals used.

Example 1 Development-inhibiting effect / eating test Test animals: Plutella maculinennis (caterpillars in the 4th

Stage of development) Number of test animals: 20 test animals: Phaedon cochleariae (larvae in the 4th

Stage of development) Number of test animals: 20 forage plants: Cabbage plants (Brassica olearacea) Solvent: parts by weight Emulsifier: part by weight To produce an appropriate preparation of active ingredient, 2 parts by weight are mixed Active ingredient with the specified amount of solvent, emulsifier and as much water that a 1% Yischllng arises, which with water to the desired concentrate is diluted.

The test animal are with leaves of the forage plants, which with a uniform spray coating of the active compound preparation are so overwound that the desired Active ingredient concentration (amount of active ingredient per unit area) reached on the leaves is fed until the image develops.

Only a solvent and emulsifier-water mixture can be used for the font roll the appropriate concentration coated leaves fed.

In this test, for example, the following compounds of the preparation examples show superior effect compared to the state of the art. 2, 8, 9, 11, 14, 17.

Example 2 Development-inhibiting effect / contact test test animal: Dysdercus intermedius (larvae in the 3rd stage of development) Number of test animals: 10 pieces Food: Cotton seeds (Gossypium hirsutum) Solvent: parts by weight Emulsifier: Part by weight To produce an appropriate preparation of active ingredient, mixing is carried out 2 parts by weight of active ingredient with the specified amount of solvent, emulsifier and so much water that a 1 dough mixture is formed, which with water to the desired Concentration is diluted.

The test animals are incorporated into the preparation of the active compound of the desired concentration immersed for 3 seconds and then caged and treated with untreated Cotton seeds and water fed.

Only a solvent and emulsifier-water mixture are used as a control animals immersed in the appropriate concentration and kept in the same way fed.

In this test, for example, the following compounds of the preparation examples show superior effect compared to the state of the art: 2, 7, 4, 7, 12, 15, 17.

Example 3 Development-inhibiting effect / Laphygma-vest test animals: Laphygma frugiperda (caterpillars) Food: 1 cm thick slices of 3 in diameter air-dried Artificial feed made from bean kernel meal, yeast, vitamin mixture, leaf powder, agar and preservative Solvent: 10 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 2 parts by weight are mixed Active ingredient with the specified amount of solvent, emulsifier and enough water that a 1 dough mixture is formed, which with water to the desired concentration is diluted.

One test animal in each case is treated with a preparation containing 1.5 ml of active ingredient the desired concentration indicated feed disc and set until hatching the imago is watching.

As a control, one test animal is placed on a 1.5 m and an emulsifier-water mixture of the appropriate concentration moistened feed disc set and observed until the imago hatches.

In this test z.S. the following compounds of the preparation examples superior effect compared to the state of the art: 4, 8, 10, 12, 16 example 4 Development-inhibiting effect / Ceratitis egg test Test animal Ceratitis capitata (Eggs) Number of test animals: 20 pieces Food: Artificial food (carrot powder with yeast powder) Solvent: parts by weight Emulsifier: parts by weight To prepare a suitable Active ingredient preparation is mixed 4 parts by weight of active ingredient with the specified Amount of solvent, emulsifier and so much water that a 1% solution is formed, which is diluted with water to the desired concentration.

The eggs of the test animals are placed on a bowl with artificial food, is incorporated into the active compound preparation so much that the desired amount is achieved in ppm (parts per million). It will develop to hatch watching the flies.

Only a solvent and emulsifier-water mixture is used as a control The appropriate concentration offered mixed artificial feed.

In this test, for example, the following compounds of the preparation examples show superior effect compared to the state of the art: 4, 9, 10.

General manufacturing processes: a) 0.1 mol of 3- (3.4-methylenedioxyphenyl) -propanediol-1 .2 is with 0.1 mol of the corresponding carbonyl compound with 0.5 g of p-toluenesulfonic acid in 300 ml of benzene on a water separator, boiled to completion the reaction. It is cooled and washed with dilute to remove the catalyst Sodium hydroxide solution, then neutral with water, dries over Na2S04, absorbs the solvent off and distilled.

b) 0.1 mol of 3,4-methylenedioxybenzyl-ethylene oxide is mixed with 0.5 mol of carbonyl compound mixed. With the addition of a few drops of boron trifluoride etherate, a strong effect occurs An exothermic reaction, which is caused by cooling with an ice bath between 50 and 1000C can be held.

After subsidence, the mixture is stirred for a further 1 hour at 60 ° C. and taken with toluene on, washes neutral with water, dries over Na2S04, removes the solvent and distilled.

According to this manufacturing process, the following compounds are obtained: At- R1 R2 manufacturing boiling point yield play path 3 Ammi g% 2 No. 1 CH3 CH3 b 140/3 72 2 -CH -C? I2-CII2H2-CH2 b 174/3 71 3 HC: 2H5 b 162/4 71 4 H C65 b 230/3 27 5 CH3 <m2 left b 160/4 48 6 H a 132/3 56 7 H i-C3H7 b 120 / 0.01 49 8 C113 i C3H1 b 124 / O, Ot 27 8 CH3 i C3 7 a 124 / 0.01 59 9 H t-C4H9 b 122 / 0.01 40 10 H c3 7 b 124 / ODOL 57 II H 3.4O (2 (><'6H3 b 250/3 28 12 CH3 n-C3H b 162/3 33 13 CH3 t-C4H9 b 100 / 0.1 35 14 CH3 C 6H5 b 206/4 32 15 C2H5 2H5 b 160/3 21 15 2H5 C2M5 a 160/3 63 16 <242 <2 <2 <2 bb 155 / 0.01 63 17 CH3 3 o 2, b 186/3 52 CH3 CH3

Claims (4)

Claims 1. Insecticidal agents, characterized by a content of benzodioxole derivatives of the formula (I) in which R¹ and R² can be the same or different and represent H, alkyl, alkenyl, alkynyl and aryl or R¹ and R² together represent an alkylene group. 2. Method of combating insects, characterized in that that one benzodioxole derivatives of the formula (I) according to claim 1 on insects and / or allows their living space to act. 3. Use of benzodioxole derivatives of the formula (I) according to claim 1 for the control of insects. 4. Process for the production of insecticidal and acaricidal agents, characterized in that benzodioxole derivatives of the formula (I) according to claim 1 mixed with extenders and / or surfactants.